A novel oxovanadate structural type – Synthesis, single crystal structure and magnetic properties of a mixed-valence polyoxovanadate formed by {V17O40(Cl)} and {V15O36(Cl)} clusters

A novel polyoxovanadate structural type, with an average nuclearity of V16, formed by a mixture of two different polyoxovananadates: {V15O36(Cl)} and{V17O40(Cl)} has been synthesized and characterized. The title compound, formulated as [Ni(phen)3]2{[V15O36(Cl)]0.5[V17O40(Cl)]0.5} · H2O (1) (phen = 1,10′-phenanthroline), presents two different polyoxovanadate architectures: {V15O36(Cl)} and {V17O40(Cl)}, with the last one representing a new framework type in polyoxovanadate chemistry. Here, we present the synthesis of this novel polyoxovanadate under hydrothermal conditions and its characterization by IR and XPS spectroscopies, elemental and thermogravimetric analysis, redox titration, magnetic measurements and single-crystal X-ray diffraction.

Graphical abstractA new “hexadecavanadate”, [Ni(phen)3]2{[V15O36(Cl)]0. 5[V17O40(Cl)]0.5} · H2O (phen = 1,10′-phenanthroline) (1), which contains two architectures of {V15O36(Cl)} (b) and{V17O40(Cl)} (c) has been synthesized and characterized. The{V17O40(Cl)} represents a new type of framework in polyoxovanadate chemistry. The formation of the two architectures can be described as the accommodation of two or four more V atoms in a{V13} fragment (a).Figure optionsDownload full-size imageDownload as PowerPoint slide